The efficient self-assembly and functional characterization of arrays containing multiple types of chromophores will provide a basis for the design and applications of functional photonic materials that are unobtainable using only one type of molecule. The design, synthesis, and characterization of supramolecular systems bearing two different types of porphyrinic chromophores, porphyrins and porphyrazines, are reported. Because the porphyrins and porphyrazines bear different exocyclic ligands for self-assembly by metal ion coordination, these systems require new supramolecular synthetic strategies wherein reactants are added in a specific order. These arrays display unique photophysical properties derived from the component chromophores, the metal geometry, and the supramolecular nanoarchitecture.